Material compositions for reinforcing ionic polymer composites

ABSTRACT

The invention is related to the preparation of an ionic polymer composite material comprising a protein and carbohydrate-containing vegetable material component that serves as a reinforcement agent for the composite. In preferred embodiments of the invention, the vegetable seed component is selected from the group of soy spent flakes, defatted soy flour, or soy protein concentrate with ionic polymers and the ionic polymer is carboxylated poly(styrene-butadiene). The composites have a significantly higher elastic modulus when compared with base polymer.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention is related to the preparation of an ionic polymercomposition comprising a protein and carbohydrate-containing vegetablematerial component, such as soy spent flakes, defatted soy flour, or soyprotein concentrate. The composite composition is formed byincorporating soy spent flakes, defatted soy flour, or soy proteinconcentrate composition with ionic polymers. The composites have asignificantly higher elastic modulus when compared with base polymer.

2. Description of the Prior Art

Soybean is composed of approximately 20% soybean oil, 8% hulls, and 72%defatted soy flour. Soybean also contains very little or no starch.Traditional approaches to the art of soybean processing involveappropriate preparation of the soybean prior to solvent extraction.After cracking of the beans and subsequent separation of the hull fromthe kernel portions, the cracked kernels are steam conditioned in largepressure cookers called bean conditioners that are located upstream froma flaking mill. The flaking mill functions to squeeze and impart aslight shear to the steam conditioned kernels resulting in the formationof a thin meal flake having a diameter of around 0.50 inch and athickness of about 10-16 mils. After the meal has been flaked, thetraditional approach is to route the flaked meal to a further heatprocessing step or directly to extraction processes. This further heatprocessing step may occur within a jacketed screw press conveyor withsteam being injected into the working section of the conveyor. Theflakes are there steam treated and are mechanically worked. The mealexiting the die orifices of the screw conveyor can best be described asincluding dust-like particles that are combined in the form of a pelletor pellets. After the flaked, steam treated pellets exit the secondheating step, they are sent to extraction processes includingextractors, desolventizer-toasters, dryer-cooler, meal grinding and mealstorage stations. During these processes, the meal is mixed with asolvent, such as hexane, which dissolves the soybean oil. The soybeanoil-solvent mixture is then separated from the meal particles. Thedesired soybean oil may then be isolated from the solvent solution byconventional techniques such as distillation, etc. The meal itself isdesolventized, dried and then ground and stored prior to use.

After the hulls are removed and soybean oil is extracted, the remainingmaterial is called defatted soy flour, which is composed of soy proteinand soy carbohydrate. (Protein Resources and Technology, 1978) Thedefatted soy flour usually contains more than 50 percent soy protein.The defatted soy flour can further be processed to separate soy proteinfrom soy carbohydrate. The separated soy protein usually contains morethan 90 percent protein and is called soy protein isolate. Soycarbohydrate contains a soluble fraction called whey and an insolublefraction called spent flakes. The defatted soy flour can be furthersubjected to acidic treatment to separate the whey from the protein andinsoluble carbohydrate. The remaining material after whey removal iscalled soy protein concentrate containing more than 70 percent protein.The protein and insoluble carbohydrate is then further separated byalkali treatment. An alternative process is to treat defatted soy flourin alkali condition to separate the insoluble carbohydrate first andthen separate the soy protein from the whey in acidic condition. If thealkali process is used to separate the spent flakes (mostly soycarbohydrate), the composition of spent flake is approximately 12%cellulose, 17% pectin, 14% protein, and 53% insoluble polysaccharide. Itis clear that the composition of soy carbohydrate is very different fromstarch that contains mostly amylose and amylopectin. The defatted soyflour, soy spent flake, and soy protein concentrate used in thisinvention can be defined as the mixture of soy protein and soycarbohydrate that contains 15-90% soy carbohydrate.

Protein, in general, has been suggested as a component in rubber latex.For example, U.S. Pat. No. 2,056,958 discloses a flexible floor coveringcomposition containing casein (milk protein) and rubber latex. U.S. Pat.No. 2,127,298 shows a composition consisting of protein, starch, andresinous matter for applications such as abrasive wheels and paintformulations. This patent also discloses a composition containing soyabean meal, lime, sodium fluoride, aluminum stearate, an oleo-resin,isopropyl alcohol, and dispersed rubber. However, the patent does notteach the use of soya bean meal in ionic polymers such as carboxylicacid or sulfonic acid modified rubber for modulus reinforcement. U.S.Pat. No. 2,931,845 teaches the composition of rubber-protein-glyoxal formodulus reinforcement. U.S. Pat. No. 3,113,605 teaches using a mixtureof protein and carbohydrate in rubber tires to modify frictionalproperties, such as anti-skid resistance. U.S. Pat. No. 5,446,078discloses using dry reactive melt blending of protein with polymerscontaining non-ionic maleic anhydride to form covalent bonds. The patentdoes not teach the use of a combination of soy protein and soycarbohydrate to achieve synergistic reinforcement effects in a polymermatrix. The reaction of maleic anhydride with active hydrogen functionalgroups from protein can only occur in the dry state, and the alkalineutralized maleic anhydride groups can not be used because the salt ofmaleic anhydride is not reactive. The patent also fails to teach theformation of intimate ionic complexes in aqueous phase with neutralizedcarboxylic acid functional groups, where the interaction between thereinforcing phase and the polymer matrix is an ionic interaction insteadof covalent bonding. U.S. Pat. No. 6,632,925 teaches using plant proteinand a compatibilizer in polylactide composites. However, polylactide isnot an ionic polymer because it does not contain ionic functional groupsalong the polymer backbone for it to be water dispersible. Therefore,polylactide cannot be used to form a complex with soy products in alkaliwater solution and is not suitable as a polymer matrix in the presentinvention. U.S. Pat. Nos. 4,812,550 and 4,607,089 teach the grafting ofvarious reactive monomers onto protein or modified protein with afree-radical initiator. These patents do not teach the formation ofnon-reactive ionic complex to enhance composite modulus. U.S. Pat. No.6,291,559 B1 teaches the use of modified or non-modified soy protein andpolyacrylate to thicken paper coating dispersions. There is no teachingherein of using a combination of soy protein and soy carbohydrate toachieve synergistic reinforcement effects in a polymer matrix. U.S. Pat.No. 4,185,146 teaches composite formation by reacting diisocyanate withnon-ionic polyalkylene ether polyol and solid soybean derivatives in adry state since the reaction cannot occur in the presence of water. Thispatent does not show the formation of an ionic complex in water phase.None of these references teach the use of soy spent flakes, defatted soyflour, or soy protein concentrate in the structural reinforcement ofionic polymer materials.

SUMMARY OF THE INVENTION

I have now discovered a novel composition of matter comprising an ionicpolymer and a protein and carbohydrate-containing vegetable materialcomponent. Of particular interest as the vegetable material component isa soy fraction, such as soy spent flakes, defatted soy flour, or soyprotein concentrate. The resultant composites have a significantlyhigher elastic modulus when compared with base polymer, and also haveimproved functional properties in comparison with composites of the basepolymer and carbon black.

In accordance with this discovery, it is an object of the invention toreinforce ionic polymers with a biodegradable, vegetable-based material.

It is a specific object of the present invention to provide a method forreinforcing ionic polymers by forming a complex of soy spent flake andionic polymers in aqueous phase, followed by a water removal process.

Further, it is an object of the present invention to provide a methodfor reinforcing ionic polymers by forming a complex of defatted soyflour and ionic polymers in aqueous phase, followed by a water removalprocess.

In addition, it is also an object of the present invention to provide amethod for reinforcing ionic polymers by forming a complex of soyprotein concentrate and ionic polymers in aqueous phase, followed by awater removal process.

One embodiment of the present invention includes reinforcing ionicpolymers with soy spent flakes obtained in the alkali separation processof soy protein isolate.

Another embodiment of the present invention includes reinforcing ionicpolymers with defatted soy flour obtained in an organic solventseparation process or a solventless process to remove soybean oil fromsoybean flakes.

An additional embodiment of the present invention includes reinforcingionic polymers with soy protein concentrate obtained in an acidicseparation process of defatted soy flour to remove soluble whey.

The present invention also includes ionic polymers that either aresynthesized by a copolymerization process or are modified by a polymermodification process to include ionic functional groups for forming anaqueous dispersion and forming complexes with soy spent flake ordefatted soy flour.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a plot of shear elastic modulus vs. temperature of compositesfilled with different amount of defatted soy flour (FIG. 1A), soy spentflake (FIG. 1B), soy protein concentrate (FIG. 1C), or carbon black N339(FIG. 1D). The significant extent of reinforcement is demonstrated whenthe composite moduli are compared with the modulus of ionic polymer with0% of fillers.

FIG. 2 is a plot of shear elastic modulus of composites filled withdifferent amounts of soy spent flakes, defatted soy flour, soy proteinconcentrate, soy protein isolate, or carbon black. The plot demonstratesa significant extent of reinforcement in the rubbery region occurring incomposites reinforced with soy spent flakes, defatted soy flour, or soyprotein concentrate when compared with the comparative examples of soyprotein isolate- or carbon black-reinforced composites.

FIG. 3 is a plot of shear elastic moduli of composites filled with 20%defatted soy flour (FIG. 3A), soy spent flakes (FIG. 3B), soy proteinconcentrate (FIG. 3C), or carbon black (FIG. 3D). The plot demonstratesthe change of moduli with eight cycles of dynamic strain at 1 Hz and140° C. (rubbery region).

FIG. 4 is a plot of shear elastic moduli of composites filled with 30%of defatted soy flour (FIG. 4A), soy spent flakes (FIG. 4B), soy proteinconcentrate (FIG. 4C), or carbon black (FIG. 4D). The plot demonstratesthe change of elastic moduli with eight cycles of dynamic strain at 1 Hzand 140° C. (rubbery region)

FIG. 5 is a plot of composites filled with different amounts of defattedsoy flour (FIG. 5A), soy spent flakes (FIG. 5B), soy protein concentrate(FIG. 5C), or carbon black N339 (FIG. 5D). The plot demonstrates thestress-strain behavior at 50 mm/min and 23° C. (transition zone,T_(g)+13° C.).

DETAILED DESCRIPTION OF THE INVENTION

Sources of the protein and carbohydrate-containing vegetable materialfor use herein include fractions or components of vegetable seeds,particularly oil seeds, that have been processed to remove substantiallyall of the oil. Typical oil processing procedures include pressingand/or extraction with aqueous or organic solvents, or withsupercritical fluids. The residues resulting from oil recovery steps ofvegetable seeds may include press cakes, meals, flakes, flours, proteinconcentrates and the like. The residues for use herein will contain atleast 10% protein, preferably at least 20% protein, and less than 85%protein, preferably less than 70% protein, and 15-90% carbohydrate,preferably 30-80%, all on a dry weight basis. Examples of suitableoilseeds include soybean, cottonseed, linseed, safflower, sunflower,lupine, sesame, tung, canola (rapeseed) and peanut. Of particularinterest are soybeans, and especially the soy spent flake, defatted soyflour, and soy protein concentrate.

Soy spent flakes are the residue remaining after oil, protein, and wheyextraction of flaked soybeans. When the oil is solvent-extracted, theflakes are also treated to remove residual solvent. Protein content ofsoy spent flakes is typically about 15%, on a dry weight basis.

Defatted soy flour is the ground, screened, graded product obtainedafter extracting most of the oil from sound, clean, dehulled soybeans.Soy flour is produced from finely grinding the defatted soy flakes sothat most of it passes through a number 100 screen. Grits are similarlyproduced, but constitute a coarser fraction than the flour. Proteincontents of defatted soy flakes and grits ranges from about 40-60%, dryweight basis.

Soy protein concentrate is prepared from high quality sound, clean,dehulled soybean seeds by removing most of the oil and water-soluble,non-protein constituents. Soy protein concentrate contains at least 65%protein, dry weight basis.

The preferred class of ionic polymers to be reinforced by theaforementioned vegetable material are polymers with a glass transitiontemperature below 150° C.

Ionic polymers intended for use herein include both synthetic andnatural polymers containing a sufficient number of ionic functionalgroups capable of dispersing the polymer in water to form an aqueousemulsion. Examples of suitable ionic polymers are carboxylatedpoly(styrene-butadiene), poly(ethylene-acrylic acid),poly(butadiene-acrylic acid), sulfonated ethylene-propylene-dieneterpolymer, poly(ethylene-methacrylic acid) . . . etc. Other examplesare carboxylic acid-modified urethane rubber, carboxylic acid-modifiedpolybutadiene, carboxylic acid-modified polyisoprene, carboxylicacid-modified nitrile butadiene rubber, carboxylic acid-modified butylrubber, carboxylic acid-modified fluorine-based thermoplastic elastomer,carboxylic acid-modified silicone rubber, carboxylic acid-modifiedpolyester-based thermoplastic elastomer, carboxylic acid-modifiedpolyamide-based thermoplastic elastomer, carboxylic acid-modifiedfluororubber, carboxylic acid-modified epichlorohydrin rubber,carboxylic acid-modified vinyl chloride-based thermoplastic elastomer,carboxylic acid-modified norbornene rubber, carboxylic acid-modifiedstyrene-based thermoplastic elastomer, carboxylic acid-modifiedolefin-based thermoplastic elastomer, carboxylic acid-modifiedurethane-based thermoplastic elastomer, and carboxylic acid-modifiedpolysulfide rubber.

Anionic polymers made by the copolymerization of monomers containingcarboxylic acid or sulfonic acid groups are suitable to form complexeswith soy spent flake, defatted soy flour, or soy protein concentrate.Examples of carboxylic acid-containing monomers are methacrylic acid,acrylic acid, fumaric acid, maleic acid, tartaric acid, itaconic acid,and crotonic acid. An examples of sulfonic acid-containing monomers isethylene sulfonic acid.

Anionic polymers made by chemical modification of existing polymers arealso suitable for this application. Examples of this class of ionicpolymers are the reaction products of alkali hydrolysis of esters of theaforementioned carboxylic acid-containing monomers. Another class ofionic polymers results from the direct sulfonation of aromatic and/orunsaturated polymers. Other carboxylic acid-modified polymers arecarboxylic acid-modified liquid isoprene rubber latex, carboxylicacid-modified isoprene rubber latex, carboxylic acid-modifiedstyrene-butadiene rubber latex, carboxylic acid-modified natural rubberlatex, carboxylic acid-modified butadiene rubber latex, carboxylicacid-modified acrylonitrile-butadiene rubber latex, carboxylicacid-modified chloroprene latex, carboxylic acid-modified acryl rubberlatex, carboxylic acid-modified acrylate-butadiene rubber latex,carboxylic acid-modified vinyl acetate rubber latex.

Copolymerizable ethylenically unsaturated monomers useful in producingthe carboxylic acid functional copolymer are monomers containingcarbon-to-carbon, ethylenic unsaturation, including vinyl monomers,acrylic monomers, allylic monomers, acrylamide monomers, and mono- anddicarboxylic unsaturated acids. Exemplary monomers are described, below.Vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrates,vinyl benzoates, vinyl isopropyl acetates and similar vinyl esters.Vinyl halides include vinyl chloride, vinyl fluoride, and vinylidenechloride. Vinyl aromatic hydrocarbons include styrene, methyl styrenesand similar lower alkyl styrenes, chlorostyrene, vinyl toluene, vinylnaphthalene, divinyl benzoate, and cyclohexene. Vinyl aliphatichydrocarbon monomers include alpha olefins such as ethylene, propylene,isobutylene, and cyclohexene as well as conjugated dienes such as 1,3butadiene, methyl-2-butadiene, 1,3-piperylene, 2,3-dimethyl butadiene,isoprene, cyclopentadiene, and dicyclopentadiene. Vinyl alkyl ethersinclude methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,and isobutyl vinyl ether. Acrylic monomers include monomers such aslower alkyl esters of acrylic or methacrylic acid having an alkyl esterportion containing between 1 to 12 carbon atoms as well as aromaticderivatives of acrylic and methacrylic acid. Useful acrylic monomerinclude, for example, acrylic and methacrylic acid, methyl acrylate andmethacrylate, ethyl acrylate and methacrylate, butyl acrylate andmethacrylate, propyl acrylate and methacrylate, 2-ethyl hexyl acrylateand methacrylate, cyclohexyl acrylate and methacrylate, decyl acrylateand methacrylate, isodecylacrylate and methacrylate, benzyl acrylate andmethacrylate, and various reaction products such as butyl, phenyl andcresyl glycidyl ethers reacted with acrylic and methacrylic acids,hydroxyl alkyl acrylates and methacrylates such as hydroxyethyl andhydroxypropyl acrylates and methacrylates.

Carboxylic acid functional polymers contemplated herein comprisecopolymerized monomers including carboxylic acid monomers that mayinclude methacrylic acids, acrylic acid, and olefinic unsaturated acids.Acrylic acids include acrylic and methacrylic acid, ethacrylic acid,alpha-chloracrylic acids, alpha-cyanoacrylic acid, crotonic acid, andbeta-acryloxy propionic acid. Olefinic unsaturated acids include fumaricacid, maleic acid or anhydride, itaconic acid, citraconic acid,mesaconic acid, muconic acid, glutaconic acid, aconitic acid,hydrosorbic acid, sorbic acid, alpha-chlorosorbic acid, cinnamic acid,and hydromuconic acid. On a weight basis, the carboxylic acid functionalpolymer contains at least 1% copolymerized carboxyl functional monomersand preferably between 5% and 15% carboxylic acid monomers, with thebalance being other ethylenically unsaturated monomers. Carboxylic acidfunctional polymers preferably are produced in bulk, either in solventor by emulsion/suspension polymerization.

One class of carboxyl functional polymer comprises a polyester polymer.Polyester polymers comprise the esterification products of glycols,diols, or polyols with excess equivalents of dicarboxylic acid orpolycarboxylic acids. Linear aliphatic glycols are esterified withgreater molar amounts of aromatic dicarboxylic acid and/or linearsaturated dicarboxylic acid having between 2 and 10 linear carbon atomssuch as adipic, azelaic, succinic, glutaric, pimelic, suberic or sebacicacid to produce polyesters. Additionally, larger dicarboxylic acids,such as the dimer fatty acids, dodecanedioic acid and the like can beused. Preferred and commercially available linear saturated dicarboxylicacids are adipic, azelaic, dodecane-dicarboxylic acid and the dimerfatty acids. Aromatic dicarboxylic acids (anhydrides) include phthalic,isophthalic, terephthalic, and tetrahydrophthalic. Minor amounts ofpolyfunctional acid such as trimelletic acid can be added. Suitableglycols include linear aliphatic glycols having 2 to 8 carbon atoms,such as 1,3- or 1,4-butylene glycol, 1,6-hexane diol, neopentyl glycol,propylene glycol, ethylene glycol and diethylene glycol, propylene, anddipropylene glycol, and similar linear glycols. Additionally, the largerdiols such as hydrogenated bisphenol A, and the C₁₀ to C₁₈ diols aresuitable. Preferred glycols are hydrophobic glycols such as neopentylglycol and 1,6-hexane diol and hydrogenated bisphenol A. Minor amountsof polyols can be used such as glycerol, pentaerythritol,dipentaerythritol, or trimethylol ethane or propane. The molardeficiency of the glycol over the greater molar amounts of aromatic andlinear saturated dicarboxylic acid is between about 1 and 50 andpreferably between about 5% and 20%. Hence, the polyester contains aconsiderable excess of unreacted carboxylic groups to provide a carboxylpolyester having an Acid No. between 5 and 300 and preferably between 20and 100. Glycol can be esterified with minor amounts of up to about 20%by weight of unsaturated dicarboxylic acids (anhydrides) includingmaleic, fumaric or itaconic acids; or monocarboxylic acids such asacetic, benzoic, and higher chain aliphatic and aromatic acids up toabout 12 carbon atoms. The polyester component can be produced bysolvent or bulk polymerization although bulk polymerization ispreferred. The raw materials can be charged in bulk and esterificationpolymerized at temperatures typically between 170° C. to 240° C.,although moderately higher or lower temperatures can be utilizedsatisfactorily with appropriate adjustment in the reaction time aswithin the skill of a person in the art. An esterification catalyst canbe used, typically at less than 1% levels based on charge, such as anorganic tin compound or organic titanate.

Another class of carboxyl polymer contemplated for use in this inventionis a carboxyl functional polymer comprising acrylic grafted polyester.Grafted copolymers of polyester and acrylics can be produced byfree-radical polymerization of ethylenically unsaturated monomers,including acrylic and carboxyl monomers, in the presence of a preformedmolten or fluid polyester at temperatures sufficient to induce additioncopolymerization of the monomers along with some grafting onto thepolyester backbone. The acrylic polymer component of the acrylic graftedpolyester comprises in-situ copolymerized ethylenically unsaturatedmonomers, including acrylic monomers and carboxyl monomers, along withother ethylenically unsaturated monomers if desired. Acrylic monomersinclude monomers such as lower alkyl esters of acrylic or methacrylicacid having an alkyl ester portion containing between 1 to 12 carbonatoms as well as aromatic derivatives of acrylic and methacrylic acid.Useful acrylic monomers include, for example, acrylic and methacrylicacid, methyl acrylate and methacrylate, ethyl acrylate and methacrylate,butyl acrylate and methacrylate, propyl acrylate and methacrylate,2-ethyl hexyl acrylate and methacrylate, cyclohexyl acrylate andmethacrylate, decyl acrylate and methacrylate, isodecylacrylate andmethacrylate, benzyl acrylate and methacrylate, and various reactionproducts such as butyl, phenyl, and cresyl glycidyl ethers reacted withacrylic and methacrylic acids, hydroxyl alkyl acrylates andmethacrylates such as hydroxyethyl and hydroxypropyl acrylates andmethacrylates. Acrylic acids include acrylic and methacrylic acid,ethacrylic acid, alpha-chloroacrylic acid, alpha-cycanoacrylic acid,crotonic acid, beta-acryloxy propionic acid, and beta-styryl acrylicacid. Other ethylenically unsaturated monomers have been previouslydescribed herein. The copolymerized monomers for the acrylic componentof the acrylic grafted polyester comprises copolymerized monomers, on aweight basis between 1% and 100% acrylic monomer, between 0% and 30%carboxylic acid containing monomer, with the balance being otherethylenically unsaturated monomers. Preferred acrylic componentscomprise on a weight basis between 20% and 90% acrylic monomer, between5% and 15% carboxyl acid monomer, with the balance being otherethylenically unsaturated monomers. It should be noted that the carboxylfunctionality could be part of the polyester polymer or part of thegrafted acrylic polymer or both polymers. The acrylic grafted polyesterpreferably comprises by weight between 10% and 70% polyester polymercomponent and between 30% and 90% acrylic polymer component.

Another class of carboxyl polymers for use herein is carboxyl functionalurethanes that can be produced by co-reacting diisocyanates with a diolor a polyol and a hydroxyl acid. Linear polyurethanes are obtained fromdifunctional reactants while branched polyurethanes are produced fromthe combination of difunctional and higher functional reactants.Urethanes for ionomeric crosslinking in composites can be prepared fromany of several available aromatic, aliphatic, and cycloaliphaticdiisocyanates and polyisocyanates. Suitable polyisocyanates can be di-or triisocyanates such as, for example, 2,4- and 2,6-tolylenediisocyanates, phenylene diisocyanate; hexamethylene or tetramethylenediisocyanates, 1,5-naphthalene diisocyanate, ethylene or propylenediisocyanates, trimethylene or triphenyl or triphenylsulfonetriisocyanate, and similar di- or triisocyanates or mixtures thereof.The polyisocyanate can be generally selected from the group ofaliphatic, cyclo-aliphatic and aromatic polyisocyanates such as forexample hexamethylene 1,6-diisocyanate, isophorone diisocyanate,diphenylmethane diisocyanate 2,4-tolylene diisocyanate, 2,6-tolylenediisocyanate and mixtures thereof, polymethylene polyphenylpolyisocyanate, or isocyanate functional prepolymers. Preferreddiisocyanates include isophorone diisocyanate, hexamethylenediisocyanate, toluene diisocyanate and the like.

A wide variety of diols and polyols can be used to prepare urethaneswith a wide range of properties. Polyethers, such as thepolytetramethylene oxides can be used to impart flexibility as well asthe polyethylene oxides and polypropylene oxides. Simple diols that canbe used include neopentyl glycol, 1,6 hexane diol, and longer chaindiols having 12-, 14- and higher carbon chains. Branching can beintroduced with polyols such as trimethylol propane and pentaerythritol.Hydroxyl functional polyesters and various other hydroxyl functionalpolymers are also suitable. Useful polyols preferably contain two,three, or four hydroxyl groups for co-reaction with the free isocyanategroups. Useful polyols are: diols such as ethylene glycol, propyleneglycols, butylene glycols, neopentyl glycol, 14-cyclohexane dimethanol,hydrogenated bisphenol A, and the like; triols such as glycerol,trimethylol propane, trimethylol ethane; tetrols such aspentaerythritol; hexols such as sorbitol, dipentaerythritol, and thelike; polyether polyols produced by the addition of alkylene oxides topolyols; polycaprolactone polyols produced by the addition of monomericlactones to polyols, such as caprolactone; and hydroxyl terminatedpolyesters.

The polyurethane copolymers suitable for use herein further contain aco-reacted hydroxy-acid material. The hydroxy-acid contains at least onereactive hydroxy group for co-reacting with the isocyanate duringpolymer synthesis and at least one non-reactive carboxy group which isessentially non-reactive to the isocyanate groups during the polymersynthesis. Examples of alkyl acids are 2,2 dihydroxymethyl propionicacid, 2,2-dihydroxymethyl butyric acid, glycolic acid, and the like;other acids are lactic acid, 12-hydroxy stearic acid, the product of theDiels-Alder addition of sorbic acid to di-(2-hydroxyethyl) maleate orfumarate, or low molecular weight (300 to 600) precondensates of polyolswith tribasic acids such as trimelletic anhydride or ricinoleic acid.Acid functionality can be introduced with materials like12-hydroxystearate, dimethylolpropionic acid, and various other hydroxyacids. Monohydroxyl acids will position the acid functionality at theend of the chain, while the diol acids will randomly place the acidgroups at intermediate positions within the chain. When isocyanates arereacted with diols and polyols of various types, the reaction rate maybe enhanced by the use of catalysts. Common isocyanate catalysts aresuitable, and examples include dibutyltindilaurate, dibutyltinoxide, andthe like.

A different class of ionic polymer that is also suitable for use in thecurrent invention is the sulfonic acid-containing polymers. Thesepolymers can be made by copolymerizing a sulfonic acid-containingmonomers. Typical examples of sulfonate-containing monomers suitable inthe practice of the present invention include alkali metal salts ofstyrene sulfonic acid, vinyl sulfonate, and acryloamidopropane sulfonicacid. Sulfonic acid groups can also be introduced by the directsulfonation of aromatic and/or unsaturated polymers. For example, thesulfonation can be made using acetyl sulfate or a combination of aceticanhydride and sulfuric acid at ambient or elevated temperatures. Afterthe sulfonation, the reaction can be terminated by alcohol or water.

Still another class of ionic polymer is the non-covalent complex ofhydrophobic polymer with surfactants that contain carboxylic acid orsulfonic acid functional groups. The hydrophobic polymers suitable forthis class of complex are the aforementioned ionic polymers without theincorporation of ionic monomers or ionic functional groups. Examples ofsurfactants suitable for the formation of the complex are fatty acidsand their salts such as lauric acid, mystric acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid, or a mixturethereof. The examples of sulfonic acid containing surfactants are linearalkylbenzene sulfonic acid, fatty alcohol sulfate, fatty alcohol ethersulfate, or their mixtures.

The level of addition of the vegetable material may be greater than2.5%, 5%, 10%, 15%, 20%, 30%, 40%, or 50% of the total amount ofvegetable material and ionic polymer on a dry weight basis. Typically,the level of addition will be in the range of about 10-30% by weight ofthe total of these two components.

For the polymer material reinforcement, it is necessary for thereinforcing material to be more rigid than the polymer to be reinforced.The soy products described herein, including soy spent flake, defattedsoy flour, and soy protein concentrate yield composites having highelastic modulus and improved stress-strain behavior, and therefore aresuitable for such applications. Relative to composites that arereinforced with carbon black or with vegetable material comprised of atleast 90% (dry weight basis) of protein, the composites of thisinvention are characterized by a higher elastic modulus.

As previously mentioned, soy spent flakes obtained from the alkaliseparation process are suitable for use in the current invention. Thealkali separation process involves the dispersion of defatted soy flourin water at alkali pH that is adjusted using strong base, such as sodiumhydroxide or potassium hydroxide. After heat treatment at 40-60° C. todisperse the soy protein, the spent flakes can be separated bycentrifugation. The dispersed soy protein remains in the aqueous phase,while spent flakes precipitate under the centrifugal force.

Defatted soy flour obtained from either an organic solvent separationprocess or from a solventless process is suitable for use in the currentinvention. For example, defatted soy flour obtained from hexaneextraction process of de-hulled and flaked soybean to remove soybeanoil, as described previously, may be used. Soy protein concentrateobtained from the acidic separation process of defatted soy flour byremoving the water-soluble whey is also suitable for use herein.

In making the composites of the invention, the vegetable matter is firstdispersed in water under alkaline conditions so as to solubilize theprotein. The pH conditions of the dispersion should be adjusted to atleast about pH 7.5, and more typically pH 9.0 or greater. Thereafter,the ionic polymer is thoroughly blended into the dispersion at ambienttemperature. The mixing time is usually less than 30 minutes due to thelow viscosity of the mixture. The dispersion is then dewatered and thecomplex solidified by any appropriate means as known in the art. Forinstance, the dispersion can be casting into a film, bar, or the like,during which process the water is expelled from the composite duringsetting of the cast. In another embodiment of the invention, thedispersion can be acidulated so as to coagulate the composite material.The acid-coagulated co-precipitate is then separated from the aqueousmedium by centrifugation, screening, or the like. The coagulatedmaterial may further be dewatered by banding on a rubber mill oraromatic fluid bed dryer at elevated temperatures.

Other components may be added to the resultant composite material priorto or after solidification, depending on the prospective end-useapplication. These components include, but are not limited to, biocide,colorant, surfactant, other filler, anti-foam agent, cross-linkingagent, UV-protectants, plasticizer, oil, antioxidant, softening agent,cross-linking or vulcanization accelerator, and the like. It is alsounderstood that proportions, components, and the manner and order ofadding the components may be varied over a wide range depending on anumber of factors such as the end-use application for the resultingformulation.

Biocides are important for stability of the aqueous dispersion ofvegetable matter and/or ionic polymer if the dispersion is to be heldfor a substantial period of time prior to processing. Biocides may alsobe important because of residual moisture that may be initially presentafter solidification of the complex, and also due to the potential forhydroscopic absorption of moisture during storage and use of the bulkmaterial or end product. The biocide can be present in any effectiveamount to improve the stability of aqueous dispersion or product,typically, an amount exceeding about 0.1% by weight, and usually in therange of 0.1% to about 1% on a dry weight basis of the solid complex.The biocide is preferably added during the mixing process of vegetablematerial with the aqueous dispersion of ionic polymers. Generally,anionic and non-ionic types of biocide are preferred.

Examples of anionic biocides include: anionic potassiumN-hydroxymethyl-N-methyl-dithiocarbamate; an anionic blend ofN-hydroxymethyl-N-methyl dithiocarbamate (80 percent by weight) andsodium 2-mercapto benzothiazole (20 percent by weight); an anionic blendof sodium dimethyl dithiocarbamate, 50 percent by weight, and (disodiumethylenebis-dithiocarbamate), 50 percent by weight; an anionic blend ofNomethyldithiocarbamate, 60 percent by weight, and disodiumcyanodithioimidocarbonate, 40 percent by weight; an anionic blend ofmethylene bis-thiocyanate (33 percent by weight), sodiumdimethyl-dithiocarbamate (33 percent by weight), and sodium ethylenebisdithiocarbamate (33 percent by weight); sodium dichlorophene (G-4-40available from Givaudan Corporation); and the like, as well as mixturesthereof.

Examples of nonionic biocides include: 2-hydroxypropylmethanethiosulfonate; 2-(thio cyanomethyl thio)benzothiazole; methylenebis(thiocyanate); 2-bromo-4′-hydroxyacetophenone;1,2-dibromo-2,4-dicyano-butane; 2,2-dibromo-3-nitropropionamide;N-α-(1-nitroethyl benzylethylene diamine); dichlorophene (6-4 availablefrom Givaudan Corporation); 3,5-dimethyltetrahydro-2H-,1,3,5-thiadiazine-2-thione; a nonionic blend of asulfone, such as bis(trichloromethyl)sulfone and methylenebisthiocyanate; a nonionic blend of methylene bisthiocyanate andbromonitrostyrene; a nonionic blend of2-(thiocyanomethylthio)benzothiazole (53.2 percent by weight) and2-hydroxypropyl methanethiosulfonate (46.8 percent by weight); anonionic blend of methylene bis(thiocyanate) 50 percent by weight and2-(thiocyanomethylthio) benzothiazole, 50 percent by weight; a nonionicblend of 2-bromo-4′-hydroxyacetophenone (70 percent by weight) and2-(thiocyanomethylthio)benzothiazole (30 percent by weight); a nonionicblend of 5-chloro-2-methyl-4-isothiazoline-3-one (75 percent by weight)and 2-methyl-4-isothiazolin-3-one (25 percent by weight), and the like,as well as mixtures thereof.

Examples of cationic biocides include: cationic poly(oxyethylene(dimethylamino)-ethylene (dimethylamino) ethylene dichloride); acationic blend of methylene bisthiocyanate and dodecyl guanidinehydrochloride; a cationic blend of a sulfone, such asbis(trichloromethyl) sulfone and a quaternary ammonium chloride; acationic blend of methylene bis thiocyanate and chlorinated phenols, andthe like, as well as mixtures thereof.

Crosslinking agents that are frequently used in rubbers are elementalsulfur and disulfides such as alkylphenol disulfides, N,N′-caprolactamdisulfides, 4,4′-dithiobismorpholine, dipentamethylene thiuramdisulfide, dipentamethylene thiuram hexasulfide, dipentamethylenethiuram tetrasulfide, dipentamethylene thiuram monosulfide, tetrabutylthiuram disulfide, tetraethyl thiuram disulfide, tetramethyl thiuramdisulfide, tetramethyl thiuram monosulfide, and the like. Variousperoxide compounds are also used, such as dicumyl peroxide,t-butylperoxy-diisobutyl benzene, di(2,4-dichloro benzoyl) peroxide,dibenzoyl peroxide, t-butylperoxy benzoate,1,1-di(t-butylperoxy)-3,3,5-trimethyl-cyclohexane,2,5-dimethyl-2,5-di(t-butylperoxy) hexane,2,5-dimethyl-2,5-di(t-butylperoxy) hexyne-3, and the like.

The following examples are provided to illustrate preferred embodimentsof the invention and are not intended to restrict the scope thereof.Unless otherwise indicated, all percentages are expressed as weightpercentages.

All references disclosed herein or relied upon in whole or in part inthe description of the invention are incorporated by reference.

EXAMPLE 1

Preparation of 10% Soy Spent Flakes Composite.

Soy spent flakes were obtained by dispersing 154 gm of defatted soyflour (Nutrisoy 7B, ADM) in 810 gm of water and cooking at pH 10 and 45°C. for 1 hour. The resulting dispersion was then centrifuged at 3000 rpmand 15° C. for 10 minutes. Soy protein dispersion was removed and thespent flakes were washed with water and centrifuged again to obtainspent flakes with a solids content of 12.2%. A 131.1 gm sample of a 7.6%aqueous dispersion of spent flakes was mixed with 177.3 gm of 50.7%carboxylated styrene-butadiene latex (CP620NA, Dow), and the pH wasadjusted to 9. The dispersion was first dried at 75° C. to a moisturecontent of 3-4% and then dried at 140° C. to a moisture content of lessthan 1%. After drying, the shear elastic moduli from −40° C. to 140° C.were measured by a dynamic mechanical method at 1 rad/s and 0.05% strain(Rheometric ARES). The effect of dynamic strain is measured at 1 Hz. Thestress-strain properties are measured by INSTRON at 50 mm/min and 23° C.The mechanical properties of this composite are shown in FIG. 1B, FIG.2, and FIG. 5B.

EXAMPLE 2

Preparation of 15% Soy Spent Flakes Composite.

Soy spent flakes were obtained by dispersing 250 gm of defatted soyflour (Nutrisoy 7B, ADM) in 1300 gm of water and cooking at pH 10 and45° C. for 1 hour. The resulting dispersion was then centrifuged at 3000rpm and 15° C. for 10 minutes. Soy protein dispersion was removed andthe spent flakes were washed with water and centrifuged again to obtainspent flakes with a solids content of 9.4%. A 209.7 gm sample of a 7.2%aqueous dispersion of spent flakes was mixed with 167.5 gm of 50.7%carboxylated styrene-butadiene latex (CP620NA, Dow) and the pH adjustedto 9. The dispersion was dried in the same manner as that in Example 1.After drying, the mechanical properties were measured as described inExample 1. The mechanical properties of this composite are shown in FIG.1B, FIG. 2, and FIG. 5B.

EXAMPLE 3

Preparation of 20% Soy Spent Flakes Composite.

Soy spent flakes were obtained by dispersing 154 gm of defatted soyflour (Nutrisoy® 7B, ADM) in 810 gm of water and cooked at pH 10 and 45°C. for 1 hour. The resulting dispersion was then centrifuged at 3000 rpmand 15° C. for 10 minutes. Soy protein dispersion was removed and thespent flakes were washed with water and centrifuged again to obtainspent flakes with a solids content of 12.2%. A 382.5 gm sample of a 5.2%aqueous dispersion of spent flakes was mixed with 157.51 gm of 50.7%carboxylated styrene-butadiene latex (CP620NA, Dow) and the pH adjustedto 9. The dispersion was dried in the same manner as that in Example 1.After drying, the mechanical properties were measured as described inExample 1. The mechanical properties of this composite are shown in FIG.1B, FIG. 2, FIG. 3B, and FIG. 5B.

EXAMPLE 4

Preparation of 30% Soy Spent Flakes Composite.

Soy spent flakes were obtained by dispersing 250 gm of defatted soyflour (Nutrisoy® 7B, ADM) in 1300 gm of water and cooked at pH 10 and45° C. for 1 hour. The resulting dispersion was then centrifuged at 3000rpm and 15° C. for 10 minutes. Soy protein dispersion was removed andthe spent flakes were washed with water and centrifuged again to obtainspent flakes with a solids content of 9.4%. A 327.4 gm sample of a 7.3%aqueous dispersion of spent flakes was mixed with 111.5 gm of 50.7%carboxylated styrene-butadiene latex (CP620NA, Dow) and the pH adjustedto 9. The dispersion was dried in the same manner as that in Example 1.After drying, the mechanical properties are measured as described inExample 1. The mechanical properties of this composite are shown in FIG.1B, FIG. 2, FIG. 4B, and FIG. 5B.

EXAMPLE 5

Preparation of 10% Defatted Soy Flour Composite.

A 10.4-gm sample of 96% defatted soy flour (Nutrisoy® 7B, ADM) wasdispersed in 220 gm of water and cooked at pH 9 and 55° C. for 1 hour.177.5 gm of 50.7% carboxylated styrene-butadiene latex (CP620NA, Dow)was added and the pH adjusted to 9. The dispersion was dried in the samemanner as that in Example 1. After drying, the mechanical propertieswere measured as described in Example 1. The mechanical properties ofthis composite are shown in FIG. 1A, FIG. 2, and FIG. 5A.

EXAMPLE 6

Preparation of 15% Defatted Soy Flour Composite.

A 15.8-gm sample of 96% defatted soy flour (Nutrisoy® 7B, ADM) wasdispersed in 250 gm of water and cooked at pH 9 and 55° C. for 1 hour.168 gm of 50.7% carboxylated styrene-butadiene latex (CP620NA, Dow) wasadded and pH adjusted to 9. The dispersion was dried in the same manneras that in Example 1. After drying, the mechanical properties weremeasured as described in Example 1. The mechanical properties of thiscomposite are shown in FIG. 1A, FIG. 2, and FIG. 5A.

EXAMPLE 7

Preparation of 20% Defatted Soy Flour Composite.

A 20.9-gm sample of 96% defatted soy flour (Nutrisoy® 7B, ADM) wasdispersed in 230 gm of water and cooked at pH 9 and 55° C. for 1 hour.158 gm of 37.9% carboxylated styrene-butadiene latex (CP620NA, Dow) wasadded and the pH adjusted to 9. The dispersion was dried in the samemanner as that in Example 1. After drying, the mechanical propertieswere measured as described in Example 1. The mechanical properties ofthis composite are shown in FIG. 1A, FIG. 2, FIG. 3A, and FIG. 5A.

EXAMPLE 8

Preparation of 30% Defatted Soy Flour Composite.

A 31.5-gm sample of 96% defatted soy flour (Nutrisoy® 7B, ADM) wasdispersed in 230 gm of water and cooked at pH 9 and 55° C. for 1 hour.140 gm of 50.7% carboxylated styrene-butadiene latex (CP620NA, Dow) wasadded and pH adjusted to 9. The dispersion dried in the same manner asthat in Example 1. After drying, the mechanical properties were measuredas described in Example 1. The mechanical properties of this compositeare shown in FIG. 1A, FIG. 2, FIG. 4A and FIG. 5A.

EXAMPLE 9

Preparation of 30% Defatted Soy Protein Concentrate Composite.

A 150.3-gm sample of 96% defatted soy flour (Nutrisoy® 7B, ADM) wasdispersed in 1200 gm of water and mixed at pH 4.5 for 0.5 hour. Thedispersion was centrifuged at 3000 rpm for 10 minutes. The washingprocess was repeated three times to obtain a soy protein concentratewith 21.9% solids content. 490 gm of water was added to 137 gm of 21.9%soy protein concentrate and cooked at pH 9 and 55° C. for 1 hour. 138.6gm of 50.7% carboxylated styrene-butadiene latex (CP620NA, Dow) wasadded and the pH adjusted to 9. The dispersion was dried in the samemanner as that in Example 1. The same process was used to preparecomposites containing 10%, 15%, and 20% of soy protein concentrate.After drying, the mechanical properties were measured as described inExample 1. The mechanical properties of this composite are shown in FIG.1C, FIG. 2, FIG. 3C, FIG. 4C, and FIG. 5C.

EXAMPLE 10 Comparative Example

Preparation of 10% Carbon Black Composite.

100-gm of carbon black grade N-339 and 3.2 gm of sodium lignin sulfonate(Vanisperse CB, LIGNOTECH USA) were homogenized at 10,000 rpm in 540 gmof water for 1 hour. The resulting carbon black dispersion had a pH of9.7 and a solid fraction of 15.9%. 63.3 gm of 15.9% carbon blackdispersion was mixed with 338 gm of 26.8% carboxylated styrene-butadienelatex (CP620NA, Dow) and the pH adjusted to 9. The dispersion was driedin the same manner as that in Example 1. After drying, the mechanicalproperties were measured as described in Example 1. The mechanicalproperties of this composite are shown in FIG. 1D, FIG. 2, and FIG. 5D.

EXAMPLE 11 Comparative Example

Preparation of 15% Carbon Black Composite.

A 100-gm sample of carbon black grade N-339 and 3.2 gm of sodium ligninsulfonate (Vanisperse CB, LIGNOTECH USA) were homogenized at 10,000 rpmin 540 gm of water for 1 hour. The resulting carbon black dispersion hada pH of 9.7 and a solid fraction of 15.9%. 75.6 gm of 15.9% carbon blackdispersion were mixed with 324.6 gm of 21% carboxylatedstyrene-butadiene latex (CP620NA, Dow) and the pH adjusted to 9. Thedispersion was dried in the same manner as that in Example 1. Afterdrying, the mechanical properties were measured as described inExample 1. The mechanical properties of this composite are shown in FIG.1D, FIG. 2, and FIG. 5D.

EXAMPLE 12 Comparative Example

Preparation of 20% Carbon Black Composite.

A 20.1-gm sample of carbon black grade N-339 and 0.78 gm of sodiumlignin sulfonate (Vanisperse CB, LIGNOTECH USA) was homogenized at10,000 rpm in 80 gm of water for 1 hour. The resulting carbon blackdispersion had a solid fraction of 20.7%. 17.6 gm of 20.7% carbon blackdispersion was mixed with 190.6 gm of 37.4% carboxylatedstyrene-butadiene latex (CP620NA, Dow) and the pH adjusted to 9. Thedispersion was dried in the same manner as that in Example 1. Afterdrying, the mechanical properties are measured as described inExample 1. The mechanical properties of this composite are shown in FIG.1D, FIG. 2, FIG. 3D, and FIG. 5D.

EXAMPLE 13 Comparative Example

Preparation of 30% Carbon Black Composite.

A 100-gm sample of carbon black grade N-339 and 3.2 gm of sodium ligninsulfonate (Vanisperse CB, LIGNOTECH USA) were homogenized at 10,000 rpmin 540 gm of water for 1 hour. The resulting carbon black dispersion hada pH of 9.7 and a solid fraction of 15.9%. 189.3 gm of 15.9% carbonblack dispersion was mixed with 190.7 gm of 37% carboxylatedstyrene-butadiene latex (CP620NA, Dow) and the pH adjusted to 9. Thedispersion was dried in the same manner as that in Example 1. Afterdrying, the mechanical properties were measured as described inExample 1. The mechanical properties of this composite are shown in FIG.1D, FIG. 2, and FIG. 4D.

EXAMPLE 14 Comparative Example

Preparation of 10% Soy Protein Isolate Composite.

A 10.5-gm sample of 95.6% soy protein isolate (Profam 781, ADM) wasdispersed in 208 gm of water and cooked at pH 9 and 55° C. for 1 hour.181 gm of 49.7% caboxylated styrene-butadiene latex (CP620NA, Dow) wasadded and the pH adjusted to 9. The dispersion was dried in the samemanner as that in Example 1. After drying, the mechanical propertieswere measured as described in Example 1. The mechanical properties ofthis composite are shown in FIG. 2.

EXAMPLE 15 Comparative Example

Preparation of 15% Soy Protein Composite.

A 15.8-gm sample of 95.4% soy protein isolate (Profam 781, ADM) wasdispersed in 220 gm of water and cooked at pH 9 and 55° C. for 1 hour.172 gm of 49.7% caboxylated styrene-butadiene latex (CP620NA, Dow) wasadded and pH adjusted to 9. The dispersion was dried in the same manneras that in Example 1. After drying, the mechanical properties weremeasured as described in Example 1. The mechanical properties of thiscomposite are shown in FIG. 2.

EXAMPLE 16 Comparative Example

Preparation of 20% Soy Protein Composite.

20.9-gm sample of 95.6% soy protein isolate (Profam 781, ADM) wasdispersed in 218 gm of water and cooked at pH 9 and 55° C. for 1 hour.161 gm of 49.7% caboxylated styrene-butadiene latex (CP620NA, Dow) wasadded and the pH adjusted to 9. The dispersion was dried in the samemanner as that in Example 1. After drying, the mechanical propertieswere measured as described in Example 1. The mechanical properties ofthis composite are shown in FIG. 2.

EXAMPLE 17 Comparative Example

Preparation of 30% Soy Protein Composite.

A 31.4-gm sample of 95.6% soy protein isolate (Profam 781, ADM) wasdispersed in 250 gm of water and cooked at pH 9 and 55° C. for 1 hour.140.9 gm of 49.7% caboxylated styrene-butadiene latex (CP620NA, Dow) wasadded and the pH adjusted to 9. The dispersion was dried in the samemanner as that in Example 1. After drying, the mechanical properties aremeasured as described in Example 1. The mechanical properties of thiscomposite are shown in FIG. 2.

EXAMPLE 18 Comparative Example

Preparation of 40% Soy Protein Composite.

A 41.8-gm sample of 95.6% soy protein isolate (Profam 781, ADM) wasdispersed in 237 gm of water and cooked at pH 9 and 55° C. for 1 hour.120.7 gm of 49.7% caboxylated styrene-butadiene latex (CP620NA, Dow) wasadded and the pH adjusted to 9. The dispersion was dried in the samemanner as that in Example 1. After drying, the mechanical properties aremeasured as described in Example 1. The mechanical properties of thiscomposite are shown in FIG. 2.

Having thus described the invention, numerous changes and modificationsthereof will be readily apparent to those having ordinary skill in theart without departing from the spirit or scope of the invention. Forexample, the compositions of the present invention also can containother fillers, colorants, stabilizers, and the like.

1. A composite comprising (1) an ionic polymer and (2) a protein andcarbohydrate-containing vegetable material.
 2. The composite of claim 1,wherein said composite is characterized by having a higher modulus whencompared with said ionic polymer alone.
 3. The composite of claim 1,wherein said vegetable material is an oilseed residue remaining afterremoval of oil from said oil seed.
 4. The composite of claim 1, whereinsaid vegetable material comprises 10-85% protein and 15-90%carbohydrate.
 5. The composite of claim 1, wherein said vegetablematerial comprises 20-70% protein and 30-80% carbohydrate.
 6. Thecomposite of claim 1, wherein said vegetable material is selected fromthe group consisting of soy spent flake, defatted soy flour, and soyprotein concentrate.
 7. The composite of claim 1, wherein said ionicpolymer contains a functional group selected from (1) carboxylic acidgroups or salts thereof; (2) sulfonic acid groups or salts thereof; and(3) mixtures of said carboxylic acids, sulfonic acids or salts thereof.8. The composite of claim 7, wherein said ionic polymer comprisespolymerized monomer units, less than 30 weight percent of which containsaid functional group.
 9. The composite of claim 8, wherein said ionicpolymer comprises at least 70 weight percent of hydrocarbon monomerunits, in addition to said monomer units containing said functionalgroup.
 10. A method for making a composite comprising: a. mixing (1) anionic polymer and (2) a protein and carbohydrate-containing vegetablematerial in the presence of water to obtain an aqueous dispersion; b.removing at least some of said water from said aqueous dispersion; andc. recovering said composite as a solid from said aqueous dispersion.11. The method of claim 10, wherein said removing of water from saidaqueous dispersion in step (b) is conducted by drying.
 12. The method ofclaim 10, wherein said removing of water from said aqueous dispersion instep (b) is conducted by reducing the pH of the aqueous dispersion atleast until said composite forms a precipitate, and separating saidprecipitate from said dispersion.
 13. The method of claim 12, whereinsaid separating is conducted by centrifugation.
 14. The method of claim13, wherein additional water is removed from said composite by drying.15. The method of claim 10, wherein said vegetable material is anoilseed residue remaining after removal of oil from said oil seed. 16.The method of claim 10, wherein said vegetable material is selected fromthe group consisting of soy spent flake, defatted soy flour, and soyprotein concentrate.
 17. The method of claim 10, wherein said ionicpolymer contains a functional group selected from (1) carboxylic acidgroups or salts thereof; (2) sulfonic acid groups or salts thereof; and(3) mixtures of said carboxylic acids, sulfonic acids or salts thereof.18. The method of claim 17, wherein said ionic polymer comprisespolymerized monomer units, less than 30 weight percent of which containsaid functional group.
 19. A product produced by the method of claim 10.20. A product produced by the method of claim
 16. 21. A product producedby the method of claim 17.